This invention relates to a process for the production of polyisocyanate silicate solid or cellular solid products by reacting a polyol silicate resinous product with a polyisocyanate to produce a polyisocyanate silicate prepolymer, then by reacting the prepolymer with a curing agent to produce a polyisocyanate silicate solid or cellular solid product. The polyol silicate resinous product is produced by reacting a silicon halide with a polyol to produce the polyol silicate resinous product.
The silicon halide may be first reacted with a fine granular silicon acid, such as hydrated silica, to produce halosilicon acids which are then reacted chemically with polyols to produce polyol silicon acid resinous product. The hydrated silica used in this process may be produced by any of the commonly known methods in the arts. Natural silicates which contain free silicic acid groups may also be used. Hydrated silica containing Si-H groups (silicoformic acid) may also be used in this invention. It is preferred that the hydrated silica be in a fine granular form.
The silicon halides which may be employed are those which have the structural formula: EQU R.sub.y SiX.sub.z
wherein X is any halogen or mixture thereof, with the preferred being chlorine; wherein R is independently selected from the group consisting of a monovalent hydrocarbon radical, a monovalent alkoxy radical, and a monovalent aryloxy radical; wherein y is an integer from 0-2, inclusive; wherein z is an integer and the sum of y plus z is equal to 4. Each of the R radicals should, preferably, although not essentially, contain less than seven carbon atoms since the compounds containing these radicals are more readily available and have been found to be the most useful. The R radicals may be the same or different. Illustrative hydrocarbon, alkoxy and aryloxy are as follows: alkyl radicals, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, etc.; alkenyl radicals, such as ethenyl, propenyl, etc.; alkynyl radicals such as ethynyl, propynyl, etc.; cycloalkyl radicals, such as cyclopropyl, cyclobutyl, cycloamyl, cyclohexyl, etc.; cycloalkenyl radicals, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, etc.; aryl radicals, such as phenyl, anthracyl, naphthyl, etc.; aralkyl radicals, such as benzyl, phenyl-ethyl, phenyl-propyl, etc.; alkaryl radicals, such as xylyl, tolyl, ethylphenyl, p-butylphenyl, p-diisobutyl phenyl, etc.; alkoxy radicals, such as methoxy, ethoxy, propoxy, etc.; and aryloxy radicals such as phenoxy, p-butylphenoxy, etc. In addition, the hydrocarbon, alkoxy or aryloxy group may be substituted with non-interfering substituents, such as halo (i.e., chloro, bromo, fluoro or iodo), nitro, sulfo, etc. The X substituent in the silicon halide is any halogen or mixture thereof, with the preference being chloride. Silicon trihalides may be used in certain cases.
Exemplificative silicon halides include, but are not limited to, the following compounds: silicon tetrachloride; silicon tetrabromide; silicon tetrafluoride; silicon tetraiodide; methyltrichlorosilane; dimethyldichlorosilane; diethyldichlorosilane; di-n-butyl-dichlorosilane; diphenyldichlorosilane; phenyltrichlorosilane; ethyl phenyldichlorosilane; methyl ethyldichlorosilane; methyl propyldichlorosilane; etc.
Silicon tetrachloride is the preferred silicon halide. The silicon tetrachloride may be utilized with any of the listed silicon halides or mixtures of the listed silicon halides.
For the purpose of this invention, the products produced by the chemical reaction of hydrated silica with a silicon tetrahalide will be called halosilicon acid; the products produced by the chemical reaction of hydrated silica with an organic halosilane will be called an organic halosilicon acid. The product produced by reaction of the halosilicon acid with a polyol will be called a polyol silicon acid. The product produced by the reaction of the polyol silicon acid with a polyisocyanate will be known as polyisocyanate silicate solid or cellular solid product. The product produced by the reaction of a silicon halide with a polyol will be known as a polyol silicate resinous product. The product produced by the reaction of a polyol silicate resinous product with a polyisocyanate will be known as a polyisocyanate silicate solid or cellular solid product.
Any suitable polyol may be used in this invention. It is preferred to use polyols, in particular, polyol compounds and/or polyol polymers which contain 2 to 8 hydroxyl groups, e.g. polyhydroxyl compounds and polyesters, polyethers, polythioesters, polyacetals, polycarbonates or polyester amides containing at least 2, generally from 2 to 8, but preferably from 2 to 4 hydroxyl groups. Polyhydroxyl compounds (polyols) which already contain urethane or urea groups, modified or unmodified natural, e.g. castor oil, carbohydrates and starches, may also be used. Additional products of alkylene oxides with phenolformaldehyde resins or urea-formaldehyde resins are also suitable for the purpose of the invention. Polybutadiene polymers with free hydroxyl groups, polysulfide polymers, polybutadiene-styrene copolymers and butadiene-acrylonitrile copolymer chains are also suitable for the purpose of the invention.
The hydroxyl group-containing polyesters (polyols) may be, for example, reaction products of polyhydric alcohol, preferably dihydric alcohols and polybasic, preferably dibasic carboxylic acids. The corresponding polycarboxylic acid anhydride or corresponding polycarboxylic acid esters of lower alcohols or their mixture may be used instead of the free polycarboxylic acids for preparing the polyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic and may be substituted, e.g. with halogen atoms and may be unsaturated. Examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethylterephthalate and bis-glycol terephthalate.
Suitable polyhydric alcohols may be used such as, for example, ethylene glycol, propylene-1,2- and -1,3-glycol, butylene -1,4- and -2,3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, cyclohexanedimethol-(1,4-bis-hydroxy-methylcyclohexane), 2-methyl-propane-1,3-diol, glycerol, trimethylol propane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, glucose, starches, fructose, cane sugar, dextrines, castor oils, methylglyoside, diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycols, dipropene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols. The polyesters may also contain a proportion of carboxyl end groups. Polyesters of lactones, such as .epsilon.-caprolactone, or hydroxycarboxylic acid, such as .omega.-hydroxy-caproic acid, may also be used.
The polyethers with at least 2, generally from 2 to 8 and preferably 2 or 3 hydroxy groups, used according to the invention, are known and may be prepared, e.g. by the polymerization of epoxides, e.g. ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin, each with itself, e.g. in the presence of BF.sub.3, or by addition of these epoxides, optionally as mixtures or successively, to starting components which contain reactive hydrogen atoms such as alcohols or amines, e.g. water, ethylene glycol, propylene-1,3'- or -1,2-glycol, trimethylol propane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine or ethylenediamine. Sucrose polyethers such as those described, e.g. in German Pat. Nos. 1,176,358 and 1,064,938 may also be used according to this invention. It is frequently preferred to use polyethers which contain primary OH groups, (up to 90% by weight, based on the total OH group content of the polyester). Polyethers modified with vinyl polymers such as those which may be obtained by polymerizating styrene or acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351; 3,304,273; 3,525,093 and 3,110,695 and German Pat. No. 1,152,536) and polybutadienes which contain OH groups are also suitable.
By "polythioethers" are meant, in particular, the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. The products obtained are polythio-mixed ethers, polythioether esters or polythioether ester amides, depending on the cocomponent.
The polyacetals used may be, for example, the compounds which may be obtained from glycols, e.g. diethylene glycol, triethylene glycol, (4,4'-dihydroxydiphenyldimethylmethane) hexanediol and formaldehyde. Polyacetals suitable for the invention may also be prepared by the polymerization of cyclic acetals.
The polycarbonates with hydroxyl groups used may be of the known kind, e.g. those which may be prepared by reacting diols, e.g. propane-1,3-diol, butane-1,4-diol and/or hexane-1,6-diol or diethylene glycol, triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g. diphenylcarbonate or phosgene.
The polyester amides and polyamides include, e.g. the predominantly linear condensates obtained from polyvalent saturated or unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.
Examples of these compounds which are to be used according to the invention have been described, e.g. in "High Polymers", Vol. XVI, "Polyurethanes, Chemistry and Technology", published by Saunders-Frisch, Interscience Publishers, New York, London, Vol. I, 1962, pages 32 to 42 and pages 44 to 54 and Vol. II, 1964, pages 5 to 6 and 198 to 199, and in Kunststoff-Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.
Any suitable polyisocyanate or polyisothiocyanate may be used in this invention. For example, arylene polyisocyanates, such as tolylene, metaphenylene, 4-chlorophenylene-1,3-, methylene-bis (phenylene-4-), biphenylene-4,4'-, 3,3'-dimethoxybiphenylene -4,4'-, 3,3'-diphenylbiphenylene-4,4'-, naphthalene-1,5-, and tetrahydro-naphthalene-1,5-diisocyanates and triphenylmethane triisocyanate, alkylene polyisocyanates such as ethylene, ethylidine, propylene-1,2-, butylene-1,4-, butylene-1,3-, hexylene-1,6-, decamethylene-1,10-, cyclohexylene-1,2-, cyclohexylene-1,4-, and methylene-bis (cyclohexyl-4,4'-) diisocyanates.
Any suitable polyisocyanate or polyisothiocyanate may be used in this invention. For example, arylene polyisocyanates, such as tolylene, metaphenylene, 4-chlorophenylene-1,3-, methylene-bis (phenylene-4-), biphenylene-4,4'-, 3,3'-dimethoxybiphenylene -4,4'-, 3,3'-diphenylbiphenylene-4,4'-, naphthalene-1,5-, and tetrahydro-naphthalene-1,5-diisocyanates and triphenylmethane triisocyanate, alkylene polyisocyanates such as ethylene, ethylidine, propylene-1,2-, butylene-1,4-, butylene-1,3-, hexylene-1,6-, decamethylene-1,10-, cyclohexylene-1,2-, cyclohexylene-1,4-, and methylene-bis (cyclohexyl-4,4'-) diisocyanates. Phosgenation products of aniline-formaldehyde condensation may be used such as polyphenyl-polymethylene polyisocyanates. Polyisothiocyanates, inorganic polyisothiocyanates, polyisocyanates which contain carbodiimide groups as described in German Pat. No. 1,092,007 and polyisocyanates which contain urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups may be used to produce polyisocyanate prepolymers or polyisocyanate organic silicate solid or cellular solid products. Mixtures of the above mentioned polyisocyanates may be used.
It is generally preferred to use commercial, readily available polyisocyanates such as toluene-2,4- and -2,6-diisocyanate and any mixture of these isomers, ("TDI"), ("crude MDI"), polyphenyl-polymethylene-isocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, and modified polyisocyanates which contain carbondiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups, ("modified polyisocyanates").
Other polyisocyanates may be used in this invention such as polyisocyanates which contain ester groups such as listed in British Pat. Nos. 956,474 and 1,086,404 and in U.S. Pat. Nos. 3,281,378 and 3,567,763, polyisocyanate reaction products with acetals according to German Pat. No. 1,072,385, polyisocyanates prepared by telomerization reactions as described in Belgian Pat. No. 723,640, polyphenyl-polymethylene polyisocyanates as described in British Patent specification Nos. 874,430 and 848,671, polyisocyanates which contain carbodiimide groups as described in German Pat. No. 1,092,007, perchlorinated arylpolyisocyanates such as those described, e.g. in German Pat. No. 1,157,601, polyisocyanates which contain allophanate groups as described, e.g. in British Pat. No. 994,890 and in Belgian Pat. No. 761,628, and the diisocyanates described in U.S. Pat. No. 3,492,330, polyisocyanates which contain biuret groups as described, e.g. in German Pat. No. 1,101,394, in British Pat. No. 889,050 and in French Pat. No. 7,017,514, polyisocyanates which contain isocyanurate groups as described, e.g. in German Pat. Nos. 1,022,789 and 1,027,394 and in British Pat. Nos. 1,091,944, 1,267,011 and 1,305,036, polyisocyanates which contain acylated urea groups according to U.S. Pat. No. 3,517,139 and polyisocyanates which contain urethane groups as described in Belgian Pat. No. 752,261 or in U.S. Pat. No. 3,394,164. Mixtures of the above polyisocyanates may be used. Organic polyisocyanates which are modified with ionic groups, for example, with carboxyl and/or carboxylate groups and/or sulphonate groups may be used with the polyisocyanates in this invention. Polyisocyanates may be reacted with alkali metal silicates such as sodium metasilicate pentahydrate, potassium metasilicate pentahydrate, dry granular crude sodium silicate and dry granular lithium silicate to produce alkali metal polyisocyanate silicate prepolymers with terminal isocyanate, used in this invention. Any of the suitable non-ionic hydrophilically modified organic polyisocyanates may be used in this invention.
Suitable polyisocyanates such as the aromatic diisocyanates may be reacted with organic compounds which contain at least two hydrogen atoms capable of reacting with isocyanates, preferably with a molecular weight of generally from 300 to about 10,000 and in the ratio of 50 to 99 mols of aromatic diisocyanate with 1 to 50 mols of said organic compounds to produce isocyanate-terminated reaction products. It is preferred to use polyols, in particular compounds and/or polymers wich contain 2 to 8 hydroxyl groups, especially those with a molecular weight of from about 800 to about 10,000 and preferably from 1,000 to about 6,000, e.g. polyesters, polyethers, polythioethers, polyacetals, polycarbonates, or polyester amides containing at least 2, generally from 2 to 8, but preferably from 2 to 4 hydroxyl groups, of the kind known for producing homogenous and cellular polyurethanes. The polyols were previously listed in this Specification.
Any suitable curing agent and/or activator may be used in this invention. The following are examples of curing agents, but are not limited to these:
1. Water. PA0 2. Water containing 10% to 70% by weight of an alkali metal silicate, such as sodium and/or potassium silicate. Crude commercial alkali metal silicate may contain other substances, e.g. calcium silicate, magnesium silicate, borates or aluminates and may also be used. PA0 3. Water containing 20 to 50% of ammonium silicate. PA0 4. Water containing 5 to 40% by weight of magnesium oxide in the form of a colloidal dispersion. PA0 5. Alkali metal metasilicate pentahydrate such as sodium silicate, potassium silicate, and commercial dry granular sodium and potassium silicate. PA0 6. Water containing 20 to 70% by weight of silica gel. PA0 7. Water containing 0.001 to 10% by weight of an activator (catalyst) such as: PA0 8. Water containing 20 to 70% by weight of a water-binding agent, being capable of absorbing water to form a solid or a gel, such as hydraulic cement, synthetic anhydrite, gypsum or burnt lime. PA0 9. Water containing 1 to 10% by weight of bases which contain nitrogen such as tetraalkyl ammonium hydroxides. PA0 10. Water containing 1 to 10% by weight of alkali metal hydroxides such as sodium hydroxide, alkali metal phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. PA0 11. Water containing 1 to 10% by weight of sodium polysulfide.
A. tertiary amines, e.g. triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-coco-morpholine, N,N,N'N'-tetramethylene-diamine, 1,4-diazo-bicyclo(2,2,2)-octane, N-methyl-N'-dimethylaminoethyl piperazine, N,N-dimethylbenzylamine, bis(N,N-diethylaminoethyl-adipate), N,N-diethylbenzylamine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-bis-tanediamine, N,N-dimethyl-beta-phenylethylamine, and 1,2-dimethylimidazole. Suitable tertiary amine activators which contain hydrogen atoms which are reactive with isocyanate groups include, e.g. triethanolamine, triisopanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, N-ethyl-diethanolamine and their reaction products with alkylene oxides, e.g. propylene oxide and/or ethylene oxide. PA1 B. organo-metallic compounds, preferably organo-tin compounds such as tin salts of carboxylic acid, e.g. tin acetate, tin octoate, tin ethyl hexoate and tin laurate and the dialkyl tin salts of carboxylic acids, e.g. dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate. PA1 C. silaamines with carbon-silicon bonds, as described in British Pat. No. 1,090,589, may also be used as activators, e.g. 2,2,4-trimethyl-2-silamorpholine or 1,3-diethylaminomethyl-tetramethyl-disiloxane. PA1 D. other examples of catalysts which may be used according to the invention and details of their action are described in Kunststoff-Handbuch, Volume VII, published by Viewig and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on page 96 and 102.
Surface active additives, (emulsifiers and foam stabilizers) may also be used according to the invention. Suitable emulsifiers are, e.g. the salts of fatty acids with amines, e.g. oleic acid diethylamine or stearic acid diethanolamine. Other surface active additives are alkali metal or ammonium salts of sulphonic acid, e.g. dodecylbenzene sulphonic acid or dinaphthyl methane disulphonic acid, or of fatty acids, e.g. ricinoleic acid, or of polymeric fatty acids.
The foam stabilizers used are mainly water-soluble polyester siloxanes. These compounds generally have a polydimethylsiloxane group attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this kind have been described, e.g. in U.S. Pat. No. 3,629,308. These additives are preferably used in quantities of from 0% to 20% by weight, based on the reaction mixture.
Negative catalysts, for example, substances which are acidic in reaction, e.g. hydrochloric acid or organic acid halides, known cell regulators, e.g. paraffins, fatty alcohols or dimethyl polysiloxanes, pigments or dyes, known flame retarding agents, e.g. tris-chloroethylphosphate or ammonium phosphate and polyphosphates, stabilizers against aging and weathering, plasticizers, fungicidal and bacteriocidal substances and fillers, e.g. barium sulphate, kieselguhr, carbon black or whiting, may also be used according to the invention.
Further examples of surface active additives, foam stabilizers, cell regulators, negative catalysts, stabilizers, flame retarding substances, plasticizers, dyes, fillers and fungicidal and bacteriocidal substances and details about methods of using these additives and their action may be found in Kunststoff-Handbuch, Volume VI, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113. The halogenated paraffins and inorganic salts of phosphoric acid are the preferred fire retardant agents.